Foodstuff and flavoring containing C1 -C6 alkyl-2-methyl-3,4-pentadienoates

ABSTRACT

Described are methods for preparing foodstuffs, flavoring compositions for foodstuffs, tobacco compositions, flavoring compositions for tobacco, perfume compositions, ingredients for perfume compositions, perfumed articles and ingredients for perfumed articles by including therein one or more C 1  -C 6  alkyl-2-methyl-3,4-pentadienoates in order to produce: 
     A. In food flavorings, sweet, fruity, strawberry, tagette oil-like, pear and/or apple-like aromas and sweet, fruity, winey, creamy, strawberry, tagette oil-like, pear and/or apple tastes; 
     B. In perfumes, berry, chamomile, wormwood, apple and/or pineapple notes; and 
     C. In tobaccos, sweet, woody and/or fruity notes; 
     As well as the novel compounds, isobutyl-2-methyl-3,4-pentadienoate and n-hexyl-2-methyl-3,4-pentadienoate.

BACKGROUND OF THE INVENTION

The present invention relates to C₁ -C₆alkyl-2-methyl-3,4-pentadienoates, more particularlyisobutyl-2-methyl-3,4-pentadienoate andn-hexyl-2-methyl-3,4-pentadienoate to alter the flavor and/or aroma ofconsumable materials, e.g., tobacco, foodstuffs, perfume compositionsand perfumed articles.

There has been considerable work performed related to substances whichcan be used to impart (or enhance) flavors to (or in) various consumablematerials. These substances are used to diminish the use of naturalmaterials, some of which may be in short supply and to provide moreuniform properties in the finished product. Sweet, fruity, winey, pear,strawberry, tagette oil-like and apple aromas as well as sweet, fruity,winey, strawberry, creamy, tagette oil-like, apple and pear tastes areparticularly desirable for many uses in foodstuff flavors. Chamomile,fruity, wormwood and strawberry notes are desirable in perfumecompositions. Fruity, sweet and woody notes are desirable in tobaccoflavoring compositions.

U.S. Pat. No. 3,499,769 issued on Mar. 10, 1970 discloses processes forimparting a fresh fruity flavor (particularly strawberry flavor) tofoods by adding a small amount of 2-methyl-2-pentenoic acid to thefoodstuff. In U.S. Pat. No. 3,499,769 it is emphasized that the basicnuance imparted by 2-methyl-2-pentenoic acid is a "berry" flavor. Quiteunexpectedly, the novel compositions of matter of the instant inventionhave properties different in kind from the 2-methyl-2-pentenoic acid ofU.S. Pat. No. 3,499,769.

Methyl-2-methyl-3,4-pentadienoate and ethyl-2-methyl-3,4-pentadienoateare known compounds, but uses of these compounds taking advantage oftheir organoleptic properties, in foodstuffs, perfume compositions,perfumed articles and/or tobacco are not disclosed in the prior art.

Synthesis of ethyl-2-methyl-3,4-pentadienoate by means of reaction ofpropargyl alcohol with triethyl orthopropionate is disclosed by Crandalland Tindell, J. Chem. Soc. D 1970 (21), 1411-12.

Synthesis of methyl-2-methyl-3,4-pentadienoate by means of reaction of3,4-pentadienoic acid with CH₂ N₂ (C₂ H₅)₂ O is disclosed by Ullman andFanshawe, J. Am. Chem. 83, 2379-83 (1961).

Japanese Patent J75,000,022 (Tanabe Seiyaku Co. Ltd.) disclosesaryl-alkyl 1,3-pentadiene-1-carboxylates useful as deodorants andantibacterial agents of the formula:

    CH.sub.3 --CH=CH--CH=CH--C(O)--O(CH.sub.2).sub.n R

(where R is phenyl, alkylphenyl, alkoxyphenyl, dialkylamino phenyl ormethylenedioxyphenyl, n is 1-3), as being prepared by condensing thecorresponding acid with an aryl alkanol of the formula:

    R(CH.sub.2).sub.n OH

in addition, British Pat. No 1,379,038 published on Jan. 2, 1975includes a broad disclosure of gamma, γ ,δ-unsaturated carbonylcompounds, useful as flavoring and odoriferous agents of the formula:##EQU1## where m is 0 or 1; n=0 and the dotted line is a bond or n=1 andthe dotted line is no bond;

R¹, r², r³, r⁴, r⁵, r⁶ and R⁷ are each H, or linear or branched(a)cyclic, (un)saturated univalent hydrocarbon or oxygen-substitutedhydrocarbon; or R⁷ with R³ or R⁴ or R⁵ may form a cycloaliphatic group,provided that R³ and R⁵ may not contain a multiple bond which isconjugated with the alpha, beta-bond) as being prepared by reacting analpha-beta-unsaturated carbonyl compound (R⁵) (R³)_(n) C=C(C)--(O)_(m)--R⁷ or halogenated carbonyl compound X(R⁵)(R³)_(n) --CH(R⁴)_(n)--C(O)--R⁷ with an organometallic compound comprising a transition metal(preferred:Cu), an univalent cation (preferred:Li⁺ ) or [Mg-Halogen]⁺and an alkenyl radical R⁶ --C(R¹)=C(R²)--, preferred in the presence ofa complexing agent e.g. diethyl ether, tetrahydrofuran,dimethoxyethane,N-tributylphosphine or trimethylphosphite.

THE INVENTION

It has now been discovered that solid and liquid footstuff and flavoringcompositions having sweet, winey, pear, strawberry, tagette oil-likeand/or apple aromas and sweet, winey, strawberry, pear-like, tagetteoil-like, apple-like and/or creamy taste notes; and novel perfumecompositions having berry, acrid, apple, wormwood, chamomile and/orpineapple notes, as well as tobacco flavoring compositions capable ofimparting a fruity and woody character to tobacco and tobacco articles,e.g., cigarettes and having aromatic, sweet and woody notes may beprovided by the utilization of isomer mixtures containing one or more C₁-C₆ alkyl-2-methyl-3,4-pentadienoates.

The C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates useful in our invention areformed by reaction of propargyl alcohol and a tri-C₁ -C₆ alkylorthopropionate in the presence of a lower alkanoic acid according tothe reaction: ##SPC1##

(wherein R is one of C₁ -C₆ alkyl, e.g., methyl, ethyl, i-butyl orn-hexyl) at pressures of from 2 up to 10 atmospheres, and temperaturesof 140°-180°C. The mole ratios of triethyl orthopropionate:propargylalcohol may vary from 1:2 up to 2:1 with a slight molar excess ofpropargyl alcohol being preferred. The lower alkanoic acid presentduring the reaction may be any acetic acid, propionic acid, butyricacid, valeric acid or isovaleric acid.

When one or more of the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates of ourinvention is used as a food flavor adjuvant, the nature of theco-ingredients included with the said C₁ -C₆alkyl-2-methyl-3,4-pentadienoates in formulating the product compositionwill also serve to alter the organoleptic characteristics of theultimate foodstuff treated therewith. As used herein, in regard toflavors, the term "alter" in its various forms means "supplying orimparting flavor character or note to otherwise bland, relativelytasteless substances or augmenting the existing flavor characteristicwhere a natural flavor is deficient in some regard or supplementing theexisting flavor impression to modify its quality, character or taste".As used herein the term "foodstuff" includes both solids and liquidsingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use being extensivelydescribed in the relevant literature. Apart from the requirement thatany such material be "ingestibly" acceptable and thus non-toxic orotherwise non-deleterious nothing particularly critical resides inselection thereof. Accordingly, such materials which may in general becharacterized as flavoring adjuvants or vehicles comprise broadlystabilizers, thickeners, surface active agents, conditioners, otherflavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2 and 3tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agaragar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches pectins, and emulsifiers, e.g., mono-anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono-and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, turmeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts, such as ferric phosphate, ferrous gluconate and the like,riboflavon, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, 4-methylpentenoic acid, 2-methyl-3-pentenoicacid; ketones and aldehydes, e.g., acetaldehyde, acetophenone, acetone,acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, beta,beta-dimethyl-acrolein, n-hexanal, 2-hexenal, cis-3-hexenal, 2-heptanal,4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols, suchas 1-butanal, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol,3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate; esters, suchas butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate,ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethyl alpha-methylbutyrate, ethyl propionate, ethyl salicylate, trans-2-hexenyl acetate,hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl acetate,isopropyl butyrate, methyl acetate, methyl butyrate, methyl capronate,methyl isobutyrate, alpha-methylbutyrate, propyl acetate, amyl acetate,amyl butyrate, pentyl-2-methyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenylglycidate, ethyl succinate, isobutylcinnamate, dimethyl benzyl carbinyl acetate, and terpenyl acetate;essential oils, such as jasmine absolute, rose absolute, oil of anise,orris absolute, lemon essential oil, Bulgarian rose, yara yara, naturalraspberry oil and vanilla; lactones, sulfides, e.g., methyl sulfide andother materials such as maltol, acetoin, acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane), andhydrocarbons (e.g., 1-methyl naphthalene and 2-methyl naphthalene).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,be capable of providing an environment in which one or more of the C₁-C₆ alkyl-2-methyl-3, 4-pentadienoates can be dispersed or admixed toprovide a homogeneous medium. In addition, selection of one or moreflavoring adjuvants, as well as the quantities thereof, will depend uponthe precise organoleptic character desired in the finished product.Thus, in the case of flavoring compositions, ingredient selection willvary in accordance with the foodstuff to which the flavor and aroma areto be imparted. In contradistinction, in the preparation of solidproducts, e.g., simulated foodstuffs, ingredients capable of providingnormally solid compositions should be selected such as various cellulosederivatives.

As will be appreciated by those skilled in the art, the amount of C₁ -C₆alkyl-2-methyl-3,4-pentadienoates employed in a particular instance canvary over a relatively wide range whereby to its desired organolepticeffects having reference to the nature of the product are achieved. Allparts and percentages given herein are by weight unless otherwisespecified. Thus, correspondingly, greater amounts would be necessary inthose instances wherein the ultimate food composition to be flavored isrelatively bland to the taste, whereas relatively minor quantities maysuffice for purposes of enhancing the composition merely deficient innatural flavor or aroma. Thus, the primary requirement is that theamount selected to be effective, i.e., sufficient to alter theorganoleptic characteristics of the parent composition, whetherfoodstuff per se or flavoring composition. Thus, the use of insufficientquantities of C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases maydisrupt the flavor-aroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, it is found thatquantities of one or more of the C₁ -C₆alkyl-2-methyl-3,4-pentadienoates ranging from a small but effectiveamount, e.g., 0.2 parts per million up to about 50 parts per million byweight based on total composition are suitable. Concentrations in excessof the maximum quantity stated are not normally recommended since theyfail to prove commensurate enhancement of organoleptic properties. Inthose instances wherein the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates isadded to the foodstuff as an integral component of a flavoringcomposition, it is of course essential that the total quantity offlavoring composition employed by sufficient to yield an effective C₁-C₆ alkyl-2-methyl-3,4-pentadienoates concentration in the foodstuffproduct.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the C₁ -C₆alkyl-2-methyl-3,4-pentadienoates in concentrations ranging from about0.015% up to about 10% by weight based on the total weight of saidflavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitjuices can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the C₁ -C₆alkyl-2-methyl-3,4-pentadienoates with for example gum arabic, gumtragacanth, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g., a vanilla powder mix ora fruit flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and C₁ -C₆alkyl-2-methyl-3,4-pentadienoates in a dry blender until the requisitedegree of uniformity is achieved.

It is presently preferred to combine with one or more of the C₁ -C₆alkyl-2-methyl-3,4-pentadienoates the following adjuvants:

Ethyl heptanoate;

Geraniol;

Palatone;

Ethyl methyl phenyl glycidate;

Diacetyl;

Styralyl acetate;

Vanillin;

Ethyl vanillin;

Geranyl acetate;

Ethyl pelargonate;

Beta ionone;

Isoamyl acetate;

δ-Undecalactone;

Cuminic acetate;

Ethyl butyrate;

Gamma undecalactone;

Naphthyl ethyl ether;

Cinnamyl isobutyrate;

Oil of anise;

Ethyl acetate;

Ethyl laurate;

Amyl butyrate;

Isoamyl butyrate;

Ethyl decylate;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxy benzene);

Ethyl isobutyrate;

Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene and

Ethyl acetoacetate

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives thereof, as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific desired sweet, fruity and woody flavorcharacteristics of natural tobacco are created or enhanced and may bereadily controlled and maintained at the desired uniform levelregardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methodswhereby various desirable sweet, fruity and woody flavoringcharacteristics may be imparted to smoking tobacco products and may bereadily varied and controlled to produce the desired uniform flavoringcharacteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials of a suitable substitute therefor (e.g., dried lettuce leaves)or we add to filters for smoking tobacco articles (e.g., celluloseacetate filters) an aroma and flavor additive containing as an activeingredient one or more C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates.

In addition to the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate of ourinvention other flavoring and aroma additives may be added to thesmoking tobacco material or substitute therefor either separately or inmixture with the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate as follows:

I. Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1,2-methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2,1-b)-furan;

4-Hydroxy hexanoic acid, gamma lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Patent3,589,372 issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil;

Origanum oil

An aroma and flavoring concentrate containing one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates and, if desired, one or more of theabove indicated additional flavoring additives may be added to thesmoking tobacco material, to the filter or to the leaf or paper wrapper.The smoking tobacco material may be shredded, cured, cased and blendedtobacco material or reconstituted tobacco material or tobaccosubstituents (e.g., lettuce leaves) or mixtures thereof. The proportionsof flavoring additives may be varied in accordance with taste butinsofar as enhancement or the imparting of natural and/or sweet notes,we have found that satisfactory results are obtained if the proportionby weight of the sum total of one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates to smoking tobacco material is between5 ppm and 100 ppm (0.0005%--0.01%) of the active ingredients to thesmoking tobacco material. We have further found that satisfactoryresults are obtained if the proportion by weight of the sum total of C₁-C₆ alkyl-2-methyl-3,4-pentadienoate used to flavoring material isbetween 50 and 1000 ppm (0.005%-0.1%).

Any convenient method for incorporating the C₁ -C₆alkyl-2-methyl-3,4-pentadienoate in the tobacco product may be employed.Thus, the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate taken alone or alongwith other flavoring additives may be dissolved in a suitable solventsuch as ethanol, pentane, diethyl ether and/or other volatile organicsolvents and the resulting solution may either be spread on the cured,cased and blended tobacco material or the tobacco material may be dippedinto such solution. Under certain circumstances, a solution of the C₁-C₆ alkyl-2-methyl-3,4-pentadienoate taken alone or taken furthertogether with other flavoring additives as set forth above, may beapplied by means of a suitable applicator such as a brush or roller onthe paper or leaf wrapper for the smoking product, or it may be appliedto the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such case, the tobacco treated may have the C₁ -C₆alkyl-2-methyl-3,4-pentadienoate in excess of the amounts orconcentrations above indicated so that when blended with other tobaccos,the final product will have the percentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is spread with a 20% ethyl alcoholsolution of ethyl-2-methyl-3,4-pentadienoate in an amount to provide atobacco composition containing 20 ppm by weight ofethyl-2-methyl-3,4-pentadienoate on a dry basis. Thereafter, the alcoholis removed by evaporation and the tobacco is manufactured intocigarettes by the usual techniques. The cigarette when treated asindicated has a desired and pleasing sweet, fruity and woody aroma whichis detectable in the main and side streams when the cigarette is smoked.This aroms is described as being sweeter, rich, less harsh, moretobacco-like and having woody, and fruity notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates of our invention can be incorporatedwith materials such as filter tip materials, seam paste, packagingmaterials and the like which are used along with tobacco to form aproduct adapted for smoking. Furthermore, one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates can be added to certain tobaccosubstitutes of natural or synthetic origin (e.g., dried lettuce leaves)and, accordingly, by the term "tobacco" are used throughout thisspecification is meant any composition intended for human consumption bysmoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

One or more of the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates and anauxiliary perfume ingredient, including, for example, alcohols,aldehydes, nitriles, esters, cyclic esters and natural essential oils,may be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance, particularly and preferably instrawberry fragrances. Such perfume compositions usually contain (a) themain note or the "bouquet" or foundation stone of the composition; (b)modifiers which round off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, the individual components will contribute itsparticular olfactory characteristics, but the over-all effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, one or more of the C₁ -C₆alkyl-2-methyl-3,4-pentadienoates can be used to alter the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition.

The amount of C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate of our inventionwhich will be effective in perfume compositions depends on many factors,including the other ingredients, their amounts and the effects which aredesired. It has been found that perfume compositions containing aslittle as 0.3% of C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate or even less(e.g., 0.05%) can be used to impart a scent odor to soaps, cosmetics orother products. The amount employed can range up to 5% of the fragrancecomponents and will depend on considerations of cost, nature of the endproduct, the effect desired on the finished product and the particularfragrance sought.

The C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate is useful in perfumecompositions as an olfactory component in detergents and soaps, spaceodorants and deodorants, perfumes, colognes, toilet waters, bathpreparations, such as bath oils, and bath solids; hair preparations,such as lacquers, brilliantines, pomades and shampoo; cosmeticpreparations, such as creams, deodorants, hand lotions and sun screens;powders, such as talcs, dusting powders, face powders and the like. Whenused as an olfactory component of a perfumed article, as little as 100parts per million of C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate willsuffice to impart a fruity, acrid, strawberry character which is one ofthe key odor characteristics of strawberry perfume formulations.Generally, no more than 2.0% of one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates based on the ultimate end product isrequired in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the C₁ -C₆alkyl-2-methyl-3,4-pentadienoate. The vehicle can be a liquid such as analcohol, a non-toxic alcohol, a non-toxic glycol, or the like. Thecarrier can also be an absorbent solid, such as a gum (e.g., gum arabic)or components for encapsulating the composition (such as gelatin).

It will thus be apparent that one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates can be utilized to alter the sensoryproperties, particularly organoleptic properties, such as flavor and/orfragrance of a wide variety of consumable materials.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I Preparation of Ethyl-2-Methyl-3,4 -Pentadienoate

Reaction: ##SPC2##

Into a 2 liter autoclave, the following materials are placed:

    ______________________________________                                        Ingredient          Amount                                                    ______________________________________                                        Triethyl orthopropionate                                                                          495 grams                                                 2-Propyn-1-ol        90 grams                                                 Propionic acid       12 grams                                                 ______________________________________                                    

The autoclave is closed and the reaction mass is heated to 150°C. over aperiod of 50 minutes. The reaction mass is then maintained at atemperature of between 135°-160°C and at a pressure of 20 up to 60 psigfor a period of 3 hours. At the end of this 3-hour period, the autoclaveis opened and the reaction mass is cooled to room temperature. 12.6 g ofsodium bicarbonate is then added to the reaction mass in order toneutralize the propionic acid. 30 g of Primol (see note 1) and 0.1 g ofTonol^(R) (see note 2) are added and the resulting reaction product isfractionally distilled at atmospheric pressure to a pot temperature of129°C. A mixture of ethanol and ethyl propionate is distilled over.Vacuum is then applied to the distillation column and the resultantproduct, ethyl-2-methyl-3,4-pentadienoate is distilled at a vaportemperature of 65°-69°C at a pressure of 24-33 mm Hg as fractions 5-10of the following fractions:

    __________________________________________________________________________    Fraction                                                                            Vapor   Liquid  Pressure                                                                            Weight of                                                                            Reflux                                     No.   Temperature                                                                           Temperature                                                                           (mm Hg)                                                                             Fraction                                                                             Ratio                                      __________________________________________________________________________    1      68-72°C                                                                        127-87°C                                                                      760    174.5 g                                                                             9:1                                        2     28-42   86-83   48-50 19.4   9:1                                        3     69      84      45    12.6   9:1                                        4     65      79      34    20.1   9:1                                        5     67      80      33    38.9   4:1                                        6     67      82      33    32.5   4:1                                        7     67      82      33    36.8   4:1                                        8     67      83      33    37.2   4:1                                        9     66      84      24    39.8   4:1                                        10    65      94      24    36.9   4:1                                        11    57      108     10    45.5   4:1                                        12    39      172     2.3   14.5   4:1                                        __________________________________________________________________________

The resulting material is confirmed by IR, NMR and mass spectralanalyses to have the structure; ##SPC3##

Mass spectral analysis:

Parent peak, then in order of decreasing intensity: m/e = 140(M⁺); 67,97, 29, 41, 125

Nuclear Magnetic Resonance Analysis:

    ______________________________________                                        ppm           Interpretation                                                  ______________________________________                                        1.26 ppm (t)  CH.sub.3 --C--O--C--                                                                            6H                                                          ∥                                                                    O                                                               1.28 ppm (d)  CH.sub.3 --C--C-- 6H                                                          ∥                                                                    O                                                               3.10 ppm (m)  =C--CH--C=O       1H                                            4.12 ppm (q)  CH.sub.3 --CH.sub.2 --O--C--                                                                    2H                                                          ∥                                                                    O                                                               4.76 ppm (m)  H.sub.2 C=C=C--   2H                                            5.40 ppm (m)  C=C=CH            1H                                            ______________________________________                                    

The nuclear magnetic resonance spectrum is set forth in FIG. 1.

Infra Red Analysis Peaks

850 cm.sup.⁻¹

1050

1175

1225

1375

1425

1730

1950

2880

2925

2975

The infra-red spectrum is set forth in FIG. 2.

At a concentration of 0.5 ppm, the resulting product,ethyl-2-methyl-3,4-pentadienoate has a fruity, strawberry, creamy aromawith berry, apple and pineapple notes and a sweet, fruity, strawberryflavor with woody and creamy nuances.

Note 1: Primol is a registered trademark identifying a hydrocarbonmineral oil produced by Exxon Corp. of Linden, New Jersey.

Note 2: Ionol is a registered trademark identifying the compound2,6-di-t-butyl-4-methyl phenol.

EXAMPLE II PREPARATION OF ETHYL-2-METHYL-3,4-PENTADIENOATE

Reaction: ##SPC4##

Into a 2 liter autoclave, the following materials are placed:

    ______________________________________                                        Ingredient          Amount                                                    ______________________________________                                        Triethyl orthopropionate                                                                          880 grams                                                                     (5 moles)                                                 2-Propyn-1-ol       336 grams                                                                     (6 moles)                                                 Propionic acid      25 grams                                                  ______________________________________                                    

The autoclave is closed and the reaction mass is heated to 160°C over aperiod of 50 minutes. The reaction mass is maintained at a temperatureof between 150°-160°C and at a pressure of 40 up to 90 psig for a periodof 3 hours. At the end of this 3-hour period, the autoclave is openedand the reaction mass is cooled to room temperature. 25.0 g of sodiumbicarbonate is then added to the reaction mass in order to neutralizethe propionic acid. 30 g of Primol and 0.1 g of Ionol are added and theresulting reaction product is distilled in a "rush-over" column yieldingthe following fractions:

    ______________________________________                                        Fraction                                                                             Vapor      Liquid     Pressure                                                                             Weight of                                 No.    Temperature                                                                              Temperature                                                                              (mm Hg)                                                                              Fraction                                  ______________________________________                                        1       37-39°C                                                                           41-43°C                                                                          100      171.0 g                                 2      42         47         100    165.3 -3 47 58 100 137.6                  4      82         98         100    179.3                                     5      114        113        100    203.4                                     6      120        150        100    217.3                                     7      75         200        100     13.7                                     ______________________________________                                    

Fractions 2-4 are combined; and 20 g Primol and 1 g Ionol are addedthereto. The resulting mixture is distilled in a 1 ft. × 1 in. Goodloedistillation column, yielding the following fractions:

    __________________________________________________________________________    Fraction                                                                            Vapor   Liquid  Pressure                                                                            Reflux                                                                             Weight of                                    No.   Temperature                                                                           Temperature                                                                           (mm Hg)                                                                             Ratio                                                                              Fraction                                     __________________________________________________________________________    1       35-104°C                                                                      102-110°C                                                                     120   19:1  24.1 g                                      2     104     110     120   9:1   6.6                                         3     104     110     120   9:1   6.1                                         4     104     110     120   9:1  21.1                                         5     105     111     120   9:1  18.6                                         6     105     111     120   9:1  18.7                                         7     105     111     120   9:1  16.7                                         8     105     111     120   9:1  19.3                                         9     105     112     120   9:1  21.4                                         10    105     112     120   9:1  15.8                                         11    104-105 112     120   9:1  25.1                                         12    105     113     120   9:1  25.0                                         13    105     114     120   9:1  21.4                                         14    105     115     120   9:1  23.0                                         15    105     117     120   9:1  23.8                                         16    105     121     120   9:1  27.6                                         17    105     130     120   9:1  28.7                                         18    105     172     120   9:1  28.5                                         19    107     181     120   9:1  11.2                                         20    108     210     120   9:1   8.9                                         __________________________________________________________________________

Fractions 9-18 are combined and confirmed to by IR, NMR and massspectral analyses to be ethyl-2-methyl-3,4-pentadienoate, having thestructure: ##SPC5##

The mass spectral analysis, nuclear magnetic resonance spectrum andinfrared spectrum are identical to those set forth in Example I and inFIGS. 1 and 2. At a concentration of 0.2 ppm, the resulting product,ethyl-2-methyl-3,4-pentadienoate has a fruity, strawberry, creamy aromawith berry, apple and pineapple notes and a sweet, fruity, strawberryflavor with woody and creamy nuances.

EXAMPLE III FLAVOR FORMULATION CONTAININGETHYL-2-METHYL-3,4-PENTADIENOATE

The following basic strawberry formulation is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Parahydroxy benzyl acetone                                                                          5                                                       Vanillin              15                                                      Maltol                20                                                      Ethyl-3-methyl-3-phenyl glycidate                                                                   15                                                      Ethyl acetate         13                                                      Ethyl butyrate        20                                                      Methyl cinnamate      5                                                       Methyl anthranilate   1                                                       Ethyl benzoate        1                                                       Gamma undecalacetone  2                                                       Diacetyl              2                                                       Anethole              1                                                       Cis-3-hexenol         20                                                      95% aqueous ethanol   180                                                     Propylene glycol      700                                                                           1000                                                    ______________________________________                                    

To a portion of the foregoing formulation, 4% by weight ofethyl-2-methyl-3,4-pentadienoate prepared according to the process ofExample I is added. The formulation with theethyl-2-methyl-3,4-pentadienoate is compared to the same formulationwithout said ethyl-2-methyl-3,4-pentadienoate.

Both flavors are evaluated in water at the rate of 50 ppm. Bothbeverages are tasted by an expert panel. The beverage containing thestrawberry formulation with the addition ofethyl-2-methyl-3,4-pentadienoate is unanimously preferred as havingfresh strawberry and a sweet-strawberry aroma and taste missing in thebasic strawberry formulation.

EXAMPLE IV TOBACCO FLAVOR FORMULATION AND TOBACCO

A tobacco mixture is produced by admixing the following materials:

    ______________________________________                                        Ingredient       Parts by Weight                                              ______________________________________                                        Bright           40.1                                                         Burley           24.9                                                         Maryland         1.1                                                          Turkish          11.6                                                         Stem (flue-cured)                                                                              14.2                                                         Glycerine        2.8                                                          Water            5.3                                                          ______________________________________                                    

Cigarettes having cellulose acetate filters are prepared from thistobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Ethyl butyrate        .05                                                     Ethyl valerate        .05                                                     Maltol                2.00                                                    Cocoa extract         26.00                                                   Coffee extract        10.00                                                   Ethyl alcohol (95% aqueous)                                                                         20.00                                                   Water                 41.90                                                   ______________________________________                                    

The above-stated tobacco flavor formulation is applied at the rate of0.1% to all of the cigarettes produced using the above tobaccoformulation. One-third of the cigarettes are then treated in the tobaccosection thereof with 5 ppm of ethyl-2-methyl-3,4-pentadienoate producedaccording to the process of Example II. One-third of the cigarettes aretreated on the cellulose acetate filter with 1 microliter of a 0.1%ethanol solution of ethyl-2-methyl-3,4-pentadienoate produced accordingto Example II.

The control cigarettes not containing the mixture having anyethyl-2-methyl-3,4-pentadienoate produced according to the process ofExample II and the experimental cigarettes which do containethyl-2-methyl-3,4-pentadienoate produced according to the process ofExample II are evaluated by three-way comparison, and the results are asfollows:

In aroma, the cigarettes containing the ethyl-2-methyl-3,4-pentadienoatein the tobacco or in the filter have been found to be sweeter andfruitier.

In smoke flavor, the cigarettes containing theethyl-2-methyl-3,4-pentadienoate are more aromatic, more sweet, fruitierand slightly less harsh in the mouth and throat. In addition, thosecigarettes containing the ethyl-2-methyl-3,4-pentadienoate in thetobacco give rise to a woody nuance in the taste and aroma on smoking.

EXAMPLE V STRAWBERRY FRAGRANCE

The following mixture is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Cuminic acetate       15                                                      Ethyl acetoacetate    3                                                       Ethyl laurate         30                                                      Cinnamyl isobutyrate  15                                                      Cinnamyl decylate     20                                                      Diacetyl (10% in 95% aqueous                                                                        2                                                       ethanol)                                                                      Ethyl pelargonate     5                                                       Gamma undecalactone   20                                                      Ethyl isobutyrate     110                                                     Ethyl isovalerate     60                                                      Ethyl heptanoate      12                                                      Dulcinyl              5                                                       2(para-hydroxyphenyl)-3-butanone                                                                    2                                                       Ethyl acetate         5                                                       Beta-ionone           5                                                       Palatone              3                                                       Vanillin              10                                                      Ethyl vanillin        10                                                      Ethyl-3-methyl-3-phenyl glycidate                                                                   70                                                      Ethyl-2-methyl-3,4-pentadienoate                                                                    10                                                      prepared according to the process                                             of Example II                                                                 ______________________________________                                    

The mixture containing ethyl-2-methyl-3,4-pentadienoate preparedaccording to the process of Example II imparts the slight acrid, berryundertone necessary to the strawberry aroma.

EXAMPLE VI PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram of the perfumecomposition of Example V until a substantially homogeneous compositionis obtained. The perfumed soap composition manifests an excellentstrawberry character with a berry undertone.

EXAMPLE VII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder is mixed with 0.15 g of theperfume composition of Example V until a substantially homogeneouscomposition is obtained. This composition has an excellent strawberryfragrance.

EXAMPLE VIII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the ethyl-2-methyl-3,4-pentadienoate preparedaccording to Example II. It has an excellent fruity, strawberry aromawith a creamy nuance.

EXAMPLE IX PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with a fruity, strawberry odor areprepared containing 0.10%, 0.15% and 0.20% ofethyl-2-methyl-3,4-pentadienoate prepared according to Example II. Theyare prepared by adding and homogeneously mixing the appropriate quantityof ethyl-2-methyl-3,4-pentadienoate in the liquid detergent. Thedetergents all possess a fruity, strawberry fragrance, the intensityincreasing with greater concentrations ofethyl-2-methyl-3,4-pentadienoate.

EXAMPLE X PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The composition of Example V is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use ofthe mixture containing ethyl-2-methyl-3,4-pentadienoate in thecomposition of Example V affords a distinct and definite strongstrawberry aroma with a fruity note to the handkerchief perfume andcologne.

EXAMPLE XI PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram ofethyl-2-methyl-3,4-pentadienoate produced according to Example II untila substantially homogeneous composition is obtained. The perfumed soapcomposition manifests an excellent strawberry aroma with a fruity note.

EXAMPLE XII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder is mixed with 0.15 g of themixture containing ethyl-2-methyl-3,4-pentadienoate of Example I until asubstantially homogeneous composition is obtained. This composition hasan excellent strawberry aroma with a fruity note.

EXAMPLE XIII

The following concentrate is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Geraniol              1.00                                                    Ethyl methyl phenyl glycidate                                                                       3.33                                                    Ethyl-2-methyl-3,4-pentadienoate                                                                    4.77                                                    (prepared according to the process                                            of Example I)                                                                 Vanillin              5.66                                                    Ethyl pelargonate     13.06                                                   Isoamyl acetate       14.00                                                   Ethyl butyrate        58.18                                                   ______________________________________                                    

EXAMPLE XIV

Another concentrate is prepared as follows:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Naphthyl ethyl ether  0.96                                                    Vanillin              2.66                                                    Ethyl methyl phenyl glycidate                                                                       2.88                                                    Ethyl-2-methyl-3,4-pentadienoate                                                                    4.90                                                    (prepared according to the process                                            of Example I)                                                                 Ethyl acetate         9.58                                                    Isoamyl acetate 12.25                                                         Ethyl butyrate        26.20                                                   Isoamyl butyrate      40.57                                                   ______________________________________                                    

EXAMPLE XV

The concentrate prepared in Example XIII is dissolved in 4 volumes ofpropylene glycol and the mixture is added to a hard candy melt at therate of 1.5 oz. of the concentrate solution per 100 lbs. of melt. Afterthe finished candy has been produced, it is found to have an excellentstrawberry flavor. When the candy is compared with candy made under thesame conditions, but without the ethyl-2-methyl-3,4-pentadienoateprepared according to the process of Example I in the concentrate, it isfound to have an inferior strawberry flavor.

EXAMPLE XVI

The propylene glycol solution of the concentrate as prepared in ExampleXV is added to a simple syrup at the rate of 1/8 oz. per gallon ofsyrup. The syrup is acidified by the addition of 1.5 oz. of 50% aqueouscitric acid solution to each gallon of syrup. A carbonated beverage isprepared by admixing one oz. of the flavored, acidified syrup with 5 oz.of carbonated water. The beverage so prepared has an excellent freshstrawberry flavor, and is found to be markedly superior to a beverageprepared in the same manner but without theethyl-2-methyl-3,4-pentadienoate prepared according to the process ofExample I.

EXAMPLE XVII

The flavor concentrate prepared in Example XIV is admixed with gumarabic and in the production of 7 lbs. of concentrate to 28 lbs. of gumarabic in 65 lbs. of water, and the aqueous mixture is spray-dried. Theflavor concentrate-carrier combination so obtained is then added to agelatin dessert mix in the ratio of 1 oz. of spray-dried material to 100lbs. of dessert mix powder. The gelatin dessert produced from the mixhas an excellent strawberry flavor and is markedly superior to a gelatindessert prepared in the same manner without theethyl-2-methyl-3,4-pentadienoate prepared according to the process ofExample II in the concentrate.

EXAMPLE XIX (A) PREPARATION OF TRIHEXYL-ORTHOPROPIONATE

Reaction: ##SPC6##

Into a three-liter distillation flask, equipped with a 2 in. splashcolumn, reflux condenser and fraction cutter, the following materialsare placed:

    ______________________________________                                        Ingredients         Amount                                                    ______________________________________                                        Triethyl ortho propionate                                                                         528 g                                                                         (3 moles)                                                 n-Hexyl alcohol     1530 g                                                                        (15 moles)                                                p-Toluene sulfonic acid                                                                           3.4 g                                                                         (0.02 moles)                                              Primol              20 g                                                      ______________________________________                                    

The reaction mass is heated to a pot temperature of 150°C at atmosphericpressure and 398.9 g of "light"(ethanol) fractions distills off. Thereaction mass is then placed under vacuum and the reaction product isdistilled over as a colorless liquid at 1.3 mm Hg pressure and atemperature of 140°-171°C. The yield is 930.7 g (87.6%) and the productis a compound having the structure: ##SPC7##

(B) PREPARATION OF n-HEXYL-2-METHYL-3,4-PENTADIENOATE

Reaction: ##SPC8##

Into a 2-liter autoclave, the following materials are placed:

    ______________________________________                                        Ingredient          Amount                                                    ______________________________________                                        n-Hexyl orthopropionate                                                                           1240 grams                                                (produced according to the                                                                        (3.5 moles)                                               process of Part A)                                                            2-Propyn-1-ol       196 grams                                                                     (3.5 moles)                                               Propionic acid      30 grams                                                  ______________________________________                                    

The autoclave is closed and the reaction mass is heated to 120°-130°C (aheatup time of 50 minutes). The reaction mass is maintained at atemperature of between 120°-130°C for a period of 5 hours. At the end ofthis 5-hour period, the autoclave is opened and the reaction mass iscooled to room temperature. 35 g of sodium bicarbonate is then added tothe reaction mass in order to neutralize the propionic acid. 40 g ofPrimol ^(R) is added and the resulting reaction product is distilled toyield ten fractions. Fractions 6, 7 and 8 distilling 95°-101°C and2.2-2.5 mm Hg (to yield 481.3 g of a crude product) are combined andfractionally distilled on a 12 in. × 1 in. Goodloe column after addingthereto 10.0 g Primol ^(R) and 0.1 g Ionol, as follows:

    __________________________________________________________________________    Fraction                                                                           Vapor   Liquid  Pressure                                                                             Weight of                                                                            Reflux                                     No.  Temperature                                                                           Temperature                                                                           (mm Hg)                                                                              Fraction                                                                             Ratio                                      __________________________________________________________________________    1    44      72-87   3.5-3.4                                                                                40.0 g                                                                             9:1                                        2    47       97     3.4    33.9   9:1                                        3    77      101     3.4    36.5   9:1                                        4    88      104     3.4    20.3   9:1                                        5    89      104     3.4    33.9   9:1                                        6    89      104     3.4    29.1   9:1                                        7    80-89   105-115 3.5-3.4                                                                              33.5   9:1                                        8    89      115     3.2    33.4   9:1                                        9    89      117     3.1    84.1   3:1                                        10   90      119     3.2    83.6   3:1                                        11   86-89   110-112 3.2    32.5   9:1                                        12   89      125     3.2    74.4   3:1                                        13   88      155     3.3    32.4   3:1                                        14   110     195     3.3    44.5   3:1                                        __________________________________________________________________________

The resulting material is confirmed by IR, NMR and mass spectralanalyses to have the structure: ##SPC9##

it has a tagette-oil-like, apple taste and aroma with pear and fattynuances.

Analyses:

1. The nuclear magnetic resonance spectrum is illustrated in FIG. 3.

2. The infrared spectrum is illustrated in FIG. 4.

3. Mass spectral analysis:

Molecular ion; then in order of decreasing intensity: 196(M⁺); 43, 41,112, 97, 67, 85.

4. NMR analysis:

    ______________________________________                                        ppm           Interpretation                                                  ______________________________________                                        0.88 ppm (t)  CH.sub.3 --CH.sub.2 --                                                                          3H                                                          C                                                                             |                                                      1.24 ppm (d)  CH.sub.3 --C--                                                                |                                                                    C=O                                                             1.28 (broad s)                                                                              --CH.sub.2 --     11H                                           1.62 (m)      --CH.sub.2 --C--O--                                                           H                                                                             |                                                      3.10 (m)      =C--C--C=O        1H                                                          O                                                                             ∥                                                      4.08 (t)      --CH.sub.2 --O--C 2H                                                          J=3Hz                                                           4.76 (7 doublets)                                                                           H.sub.2 C=C=C--   2H                                                          6Hz                                                             5.32 (q)      --C=C=CH          1H                                            ______________________________________                                    

5. Infrared analysis:

845 cm.sup.⁻¹

1065

1085

1175

1250

1455

1730

1960

2860

2880

2940

2960

Insofar as its taste is concerned, the thus produced material has sweet,fruity, strawberry and tagette oil-like aroma and flavor notes withberry, pear and winey nuances. Insofar as its usefulness in perfumes isconcerned, the thus produced material has a pear, green floral aromawith wormwood notes.

EXAMPLE XX PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of the n-hexyl-2-methyl-3,4-pentadienoate preparedaccording to Example XIX. It has an excellent long lasting fruity,apple, tagette-oil aroma with a chamomile nuance.

EXAMPLE XXI PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with a long lasting fruity, apple,tagette-oil odor are prepared containing 0.10%, 0.15% and 0.20% ofhexyl-2-methyl-3,4-pentadienoate prepared according to Example XIX. Theyare prepared by adding and homogeneously mixing the appropriate quantityof n-hexyl-2-methyl-3,4-pentadienoate in the liquid detergent. Thedetergents all possess a fruity, apple, tagette-oil-like fragrance witha chamomile nuance, the intensity increasing with greater concentrationsof n-hexyl-2-methyl-3,4-pentadienoate.

EXAMPLE XXII PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The product of Example XIX is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use ofthe n-hexyl-2-methyl-3,4-pentadienoate of Example XIX affords a distinctand definite strong tagette-oil-like aroma with an apple note and achamomile nuance to the handkerchief perfume and cologne.

EXAMPLE XXIII PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips are mixed with one gram ofn-hexyl-2-methyl-3,4-pentadienoate produced according to Example XIXuntil a substantially homogeneous composition is obtained. The perfumedsoap composition manifests an excellent tagette-oil-like aroma withapple and chamomile nuances.

EXAMPLE XXIV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 g of a detergent powder is mixed with 0.15 g of themixture containing n-hexyl-2-methyl-3,4-pentadienoate produced accordingto Example XIX until a substantially homogeneous composition isobtained. This composition has an excellent tagette-oil-like aroma witha chamomile nuance.

EXAMPLE XXV PEAR FLAVOR FORMULATION CONTAININGn-HEXYL-2-METHYL-3,4-PENTADIENOATE

The following mixture is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Vanillin              2.0                                                     Ethyl hexanoate       0.5                                                     Ethyl decanoate       1.0                                                     Benzyl acetate        0.5                                                     Ethyl octanoate       2.0                                                     Gamma undecalactone 10% (in 95%                                               ethyl alcohol)        2.0                                                     Alpha ionone 0.1% (in 95% ethyl                                               alcohol)              5.0                                                     Hexyl acetate         25.0                                                    Lemon oil, cold pressed                                                                             5.0                                                     Ethyl butyrate        7.0                                                     Ethyl acetate         40.0                                                    Butyl acetate         20.0                                                    Amyl valerate         65.0                                                    Amyl acetate          640.0                                                   Ethyl alcohol         185.0                                                   ______________________________________                                    

n-hexyl-2-methyl-3,4-pentadienoate is added at the rate of 6% to aportion of the above basic pear formulation. The other portion is left"as is". Both flavors are compared in water at the rate of 50 ppm andevaluated by a bench panel to determine that the pear flavor with theaddition of n-hexyl-2-methyl-3,4-pentadienoate has a fresh pear, winey,tagette oil-like aroma and a more full ripe pear, winey, slightly spiceytaste. The pear formulation with the n-hexyl-2-methyl-3,4-pentadienoateis preferred because it provides basic notes missing in the basic pearflavor.

EXAMPLE XXVI PREPARATION OF ISOBUTYL-2-METHYL-3,4-PENTADIENOATE

Reaction: ##SPC10##

Into a 2 liter autoclave, the following materials are placed:

    ______________________________________                                        Ingredient          Amount                                                    ______________________________________                                        Triisobutyl orthopropionate                                                                       696.9 grams                                               2-Propyn-1-ol       151 grams                                                 Propionic acid      17 grams                                                  ______________________________________                                    

The autoclave is closed and the reaction mass is heated to 140°C over aperiod of 50 minutes. The reaction mass is then maintained at atemperature of 140°C for a period of 4 hours. At the end of this 4-hourperiod, the autoclave is opened and the reaction mass is cooled to roomtemperature. 20 g of sodium bicarbonate is then added to the reactionmass in order to neutralize the propionic acid. 30 g of Primol is addedand the reaction mass is fractionally distilled on a 2 in. splash columnyielding the following fractions:

    __________________________________________________________________________         Vapor   Liquid                                                           Fraction                                                                           Temper- Temper- Pressure                                                                            Weight of                                          No.  ature   ature   (mm Hg)                                                                             Fraction                                                                             % Product                                   __________________________________________________________________________    1     38-25°C                                                                        45-27°C                                                                       30-8.7                                                                              182.1  2                                           2    30      44      6.0   192.5  4.1                                         3    70      77      6.0    55.4  14.6                                        4    72      80      6.8   213.9  93.3                                        5    72      200     7.9   131.6  97                                          __________________________________________________________________________

10 g Primol and 0.1 g Ionol are then added to the resulting distillatewhich is vacuum distilled yielding isobutyl-2-methyl-3,4-pentadienoateas follows:

    __________________________________________________________________________         Vapor   Liquid                                                           Fraction                                                                           Temper- Temper- Pressure                                                                            Weight of                                                                           Reflux                                       No.  ature   ature   (mm Hg)                                                                             Fraction                                                                            Ratio                                        __________________________________________________________________________    1     41-70°C                                                                        77-83°C                                                                       7.3-7.7                                                                             15.4  19:1-19:1                                    2    72      78      7.9   12.9  19:1                                         3    72      78      7.8   15.1  19:1                                         4    72      78      7.8   22.8  9:1                                          5    72      78      7.8   30.3  4:1                                          6    72      78      7.8   39.6  4:1                                          7    72      78      7.8   48.3  4:1                                          8    72      78      7.8   47.3  4:1                                          9    72      78      7.8   46.0  4:1                                          10   72      81      7.8   43.6  4:1                                          11   72      204     7.8    7.7  4:1                                          __________________________________________________________________________

The resulting material is confirmed by NMR and IR analyses to have thestructure: ##SPC11##

Nuclear Magnetic Resonance Analysis:

    ______________________________________                                        ppm           Interpretation                                                  ______________________________________                                        0.92 ppm (d)  CH.sub.3 H        6H                                                          ∠C--                                                                    CH.sub.3                                                        1.26 ppm (d)  C=C               3H                                                          |                                                                    CH.sub.3 --CH                                                                 |                                                                    C=O                                                             1.92 ppm (m)  H.sub.3 CH                                                                    |                                                                    ∠C--                                                                    H.sub.3 C                                                       3.12 ppm (m)  |                                                                    O=C--C--C=C       1H                                                          H                                                               3.87 ppm (d)  O                                                                             ∥                                                                    --CH.sub.2 --O--C--                                                                             2H                                            4.79 ppm (d of d)                                                                           H.sub.2 C=C=C--C  2H                                            5.33 ppm (m)  H.sub.2 C=C=C--C  1H                                                          |                                                                    H                                                               ______________________________________                                    

The nuclear magnetic resonance spectrum is set forth in FIG. 5.

Infra Red Analysis Peaks

840 cm.sup.⁻¹

985

1030

1065

1085

1170

1240

1300

1365

1375

1455

1470

1730

1955

2870

2940

2960

The infra-red spectrum is set forth in FIG. 6.

At 1 ppm this material has a winey and estery aroma and taste. At 2 ppmit has a fruity and sweet aroma and taste. At 5 ppm it is fruity andpineapple-like. At 10 ppm it has licorice-like notes, is winey.

What is claimed is:
 1. A process for altering the fruit flavor of afoodstuff which comprises adding thereto from 0.2 ppm up to about 50 ppmby weight based on the total weight of the foodstuff which is a fruitflavor augmenting amount, of a composition consisting essentially of oneor more C₁ -C₆ alkyl-2-methyl-3,4-pentadienoates.
 2. The process ofclaim 1 wherein the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate isethyl-2-methyl-3,4-pentadienoate.
 3. A fruit flavor augmentingcomposition comprising (i) from about 0.015% up to about 10% by weightof the total weight of said flavoring composition of one or more C₁ -C₆alkyl-2-methyl-3,4-pentadienoates and (ii) as a flavor adjuvant, acompound selected from the group consisting of geraniol, ethyl, methylphenyl glycidate, vanillin, ethyl pelargonate, isoamyl acetate, ethylbutyrate, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate,2-methyl-2-pentenoic acid, 4-allyl-1,2,6-trimethoxy benzene and4-propenyl-1,2,6-trimethoxy benzene.
 4. A flavoring composition of claim3 wherein the C₁ -C₆ alkyl-2-methyl-3,4-pentadienoate isethyl-2-methyl-3,4-pentadienoate.